Molecular Interactions

Electric dipole moment

1. Definition 2. Unit of dipole moments

 
  QR 1 D (debye) = 3.3564 × 10-30 C·m

Two charges of e and –e are


An electric 
dipole is composed of two charges, separated by 100 pm.
Q and –Q, separated by a distance R. The The electric dipole moment is 4.8D.
dipole moment  is defined as Q
electric 
times R , which is a vector pointing from the
negative charge to the positive one.

3. Addition

The electric dipole moment is a vector.

The addition of two dipole moments follows
res      212 cos  
2 2 1/ 2
the law of vector addition.
1 2
 Polar and nonpolar molecules
A polar molecule has a permanent dipole moment arising from
the partial charges of its atoms.
A nonpolar molecule has no permanent dipole moment.

All homonuclear diatomic molecules are nonpolar molecules.

All heternuclear diatomic molecules are polar molecules.
Whether a polyatomic molecule is polar or not
is strongly related to the geometric symmetry
of the molecule.

O3 is polar. CO2 is nonpolar.

 Dipole moments of molecules
without geometric symmetry
x   Qj x j y  Qj y j z   Qj z j
j j j

Qj is the partial charge of atom j.

xj, yj and zj are the Cartesian coordinates of atom j.

    
2
x
2
y z

2 1/ 2
Locations and partial charges of the atoms of a peptide
 Calculation : location and magnitude

(182,-87,0) H +0.18
(0,0,0)
 C
-0.36
(132,0,0) N +0.45

O
-0.38 (-62,107,0)

x = (-0.36e) x (132 pm) + (0.45e) x (0 pm)

+(0.18e) x (182 pm) + (-0.38e) x (-62 pm)
= 8.8e pm
= 8.8 x (1.602 x 10-19 C) x (10-12 m)
= 1.4 x 10-30 C m = 0.42 D

res  2.7 D 6
 Interactions between partial charges : the potential energy
of interaction

Coulomb potentials between two charges in vacuum and in a fluid

vacuum 1 q1q2 1 q1q2

V (r )  V (r ) 
4 0 r 4 r
fluid
0 : permittivity of the vacuum
 : permittivity of the matter
r : Relative permittivity of the matter


r 
0

For water at 25ºC, r=78.

V  1/r
 12
V (r ) 
4 0 r 3

1  3 cos 2

 Interaction between a dipole and a point charge

1Q2
V  , 1  Q1l
4 0 r
Electric potential energy 2

V(r) decrease with distance r as 1/r2.

 Interaction between a dipole and a point charge

Calculation for the more general orientation

is given as:
q2

1Q2 cos 
V  l r

4 0 r 2 

q1 -q1

1Q2
V  for   0, If Q2 is positive, energy is lowest,
4 0 r 2
when  = 0 (and cos  = 1),
Q attraction > repulsion
V  1 2 2 for    ,
4 0 r
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 Interactions between dipoles: dipole-
dipole interactions
Interaction energy between two dipoles µ1 and µ2:

12
V  , 1  q1l;  2  q2l
2 0 r 3

For dipole-dipole interaction the potential energy

decreases as 1/r3 (instead of 1/r2 for point-dipole)
because the charges of both dipoles seem to merge as
the separation of the dipoles increases.
 Interaction between two parallel dipoles
l2
12
V (r ) 
4 0 r 3

1  3 cos  
2

l1
q2
r
-q2


I. V(r) decrease with distance r as 1/r3. q1 -q1

II. As the two dipoles are parallel to the line

connecting them (=0 or =), V is the lowest.

21 2
V  for   0 or 
4 0 r 3

III. As the two dipoles are perpendicular

to each other (=/2), V is the highest.
12
V for    / 2
4 0 r 3
 Interactions between two rotating polar molecules

• If the two polar molecules are freely rotated, the averaged interaction
energy is zero.
• The interaction energy between them is favorable for the dipole
moments of the two molecules both parallel to the line connecting them.

The average interaction energy

2 1  2
2 2
Favorable
V (r )   direction
3(4 0 ) k BTr 2 6

Unfavorable
I. V(r) is negative so the two dipoles attract direction
each other.
II. V(r) decrease with distance r as 1/r6.
III. This is an example of the van der Waals
interaction.
 Induced dipole moment
• A nonpolar molecule may acquire a temporary induced dipole moment * by the
electric field E generated by a nearby ion or polar molecule.
• Physical reason:
Without an external electric field, the centers of the negative and positive charge
distributions are at the same place, so there is no permanent dipole moment. But,
in an external electric field, the centers of the negative and positive charge
distributions are separated by a distance.

Polarizability  of a nonpolar molecule

The polarizability depends on the orientation
*    x*   xx E x
  E  *y   yx E x
of the molecule with respect to the electric
field.
 z*   zx E x In general, the polarizability is a 3 × 3 matrix.
A large polarizability means the electronic
Polarizability volume (in unit of volume) density can undergo relatively large
fluctuation. The polarizability is inversely
 proportional to the ionization energy.
  [ ]  [V ]  L3
4 0
 Dipole-induced-dipole interaction

The interaction between a polar molecule with dipole

moment 1 and an nonpolar molecule with polarizability 2

 2 2

V (r )   1

4 0 r 6
I. The interaction energy is negative so that the force
between the two molecules is attractive.
II. V(r) decrease with distance r as 1/r6.
III. This is another example of the van der Waals
interaction.
IV. The induced dipole moment of the nonpolar molecule
will be forced to align with the dipole moment of the
polar molecule and follows the changing in orientation of
the permanent dipole moment.
 Dispersion interaction (London force)
Molecular systems:
Interactions between species that have neither a net
charge nor a permanent dipole moment, such as two
Ar atoms, two benzenes, two N2 molecules, or two
nonpolar groups of the peptide residues of a protein.

Physical picture:
As a result of fluctuation in the electronic
distribution to cause the separation of the partial
positive and negative charges, the nonpolar
molecules may posses transient dipoles . Once a 31 2 I1I 2
molecule gets a instantaneous dipole moment 1, V (r )   
this transient dipole may polarize its nearby 2r 6
I1  I 2
molecule and induce in it another transient dipole
I1 and I2 are the ionization
moment 2. The two transient dipoles are correlated
energies of molecule 1
in the same direction so that the two dipoles attract
and 2, respectively.
each other and their potential energy is lowered.
 Hydrogen bonding
The coulombic interaction between the partly
exposed positive charge of a proton bound to an
electron withdrawing X atom (in X—H) and the
negative charge of a lone pair on the second atom Y,
as in: d-A—Hd+ ……Bd-

 Strongest intermolecular interaction

 Denoted A—H……B, with A and B being N, O, or F
 only molecules with these atoms
 ‘Contact’ interaction
 turns on when X—H group is in contact with Y atom
 Dominates other intermolecular interactions
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 Comparison between molecular interactions

• All attractions in the dipole-dipole interactions, the dipole-induced-dipole

interactions and the dispersion interactions are inversely proportional to r6.
• The repulsions between molecules come from the Pauli exclusion
principle.
• The strength of the H-bond is stronger than all other van der Waals
interactions.
• The H-bonds account for the rigidity of molecular solids, like ice, and the
secondary structure of proteins.
 Hydrophobic effect
What is the hydrophobic effect? CH4 (in CCl4) → CH4 (in water)
The hydrocarbon molecules (oils and fat) and the DS = -75 JK-1 ．mol-1 increase
nonpolar molecules (CH4) are not able to dissolve in in order
water by the decrease in entropy, which is against the DH = -10 kJ．mol-1 exothermic
second law of thermodynamics. DG = 12 kJ．mol-1
The transfer of a nonpolar molecule from a nonpolar to
a polar solvent is classified as hydrophobic. This
effect that prevents from dissolving forms a solvent
cage by water molecules around the hydrocarbon
molecule, which decrease the entropy of the system.
This causes the hydrocarbon molecules to cluster
together, with larger cages, but few in number, which
results in more water molecules free to more and
increases the entropy of the whole system. The
clustering together of the hydrocarbon molecules due The hydrophobic effect is present
to the entropy consideration is the origin of the in micelles, biopolymers and the
hydrophobic interaction, which is a virtual attractive hydrocarbon groups in the
force between the solute molecules. polypeptides.
 van der Waals interactions
The interaction between two molecules at a finite distance is van der
Waals interaction, in which the interactions due to the covalent and ionic
bonds are excluded.
The van der Waals interaction is the origin of cohesion to form matters.
 The van der Waals interactions include the attractions, which arise from
the partial electric charges and electron clouds of polar and nonpolar
molecules, and the repulsions, which arise from the exclusion of electrons
from the regions where the orbitals of close-shell species overlap.
The attractions are responsible for the condensation of gases into liquids.
The repulsions prevent the continuous collapse of matter.

A picture of the interaction energy

between two closed-shell species
The interaction is attractive at large
distances and repulsive at short
distances, and has a minimum at
some distance.